Acid monoazo dyestuffs



United States PatefitO ACID MON OAZO DYESTUFFS Franz Frisch, ArlesheimBasel-Land, near Basel, and Markus Kappeler, Basel, Switzerland,assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing.Application July 6, 1954, Serial No. 441,645

Claims priority, application Switzerland July 7, 1953 6 Claims. (Cl.260-198) The present invention relates to acid monoazo dyestufis.

In accordance with the present invention, valuable monoazo dyestufis areobtained when diazotized l-amino- 4-phenoXybenzene-Z-sulfonic acids ofthe formula wherein R is a phenyl radical which is substituted by one ormore halogen atoms, alkyl groups or alkoxy groups, or is a5,6,7,S-tetrahydronaphthyl(1 or 2) radical.

Illustrative of 1-atnino-4-phenoxybenzene-2-sulfonic acids of Formula Iwhich are suitable as diazo components in the preparation of thedyestuffs of the present invention are inter alia:

1-amino-4-phenoxybenzene-Z-sulfonic acid,

1-amino-4-(2'2-chloro) -phenoxybenzene-Z-sulfonic acid,

l-amino-4-(3'-chloro)-phenoxybenzene-2-sulfonic acid,

1-amino-4-(4'-chloro)-phenoxybenzene-Z-sulfonic acid,

1-amino-4-(4-fluoro)-phenoxybenzene-2-sulfonic acid,

1 amino 4-(2,4' dichloro)-phenoxybenzene-2-sulfonic acid,

1 amino 4-(2,5'-dichloro) -phenoXybenzene-2-sulfonic acid,

1-amino-4-(2-methyl)-phenoxybenzene-2-sulfonic acid,

1-amino-4-(3-methyl) -phenoxybenzene-Z-sulfonic acid,

1-amino-4-(4'-methyl)-phenoXybenzene-2-sulfonic acid,

1-amino-4-(2'-ethyl)-phenoxybenzene-2-sulfonic acid,

1-a1nino-4-(3'-ethyl)-phen0Xybenzene-Z-sulfonic acid,

1-amino-4-(4'-ethyl) -phenoxybenzene-Z-sulfonic acid,

1 amino 4-(2,3'-dimethyl)-phenoxybenzene-Z-sulfonic acid,

1 amino 4-(2',4'-dimethyl)-phenoXybenzene-2-sulfonic acid,

1 amino 4-(2,5'-dimethyl)-phenoxybenzene-2-sulfonic 1 zfriiino4-(2',6-dimethyl) -phenoxybenzene-2-sulfonic 1 flllllO4-(3',4'-dimethyl) -phenoXybenzene-2-s ulfonic 1 51 51111104-(3',5-dimethyl) -phenoxybenzene Z-sultonic l iiiifino-44 3 '-chloro-4-methyl -phenoxybenzene-2 -sulfonic acid,

.wherein R1 and R2 have the 1 amino 4-(2'methoXy-5-methyl)-phenoxybenzene-2- sulfonic' acid,

1-amino-4- 2',4,5 '-trimethy1) -phenoxyb enzene-2-sulfonic acid,

1-amino-4- (2',4',6-trimethyl) -phenoxybenzene-2-sulfonic acid,

1-amino-4-(4'-isopropyl)-phenoxybenzene-2-sulfonic acid,

1-amino-4-(4-tert. butyl) -phenoxybenzene-2-sulfonic acid,

1-amino-4-(4'-iso-octyl)-phenoXybenzene-2-sulfonic acid,

1 amino 4-(4'-cyclohexyl)-phenoxybenzene-2-sulfonic acid,

1-amino-4-(4'-benzyl) -phenoxybenzene-Z-sulfonic acid,

1-amino-4- (4'-phenyl) -phenoxybenzene-Z-sulfonic acid,

1-amino-4-(3-methoxy)-phenoxybenzene-Z-sulfonic acid,

1 amino-4-(4-methoxy) -phenoXybenzene-2-sulfonic acid,

1-amino-4-(3-ethoxy) -phenoxybenzene-2-su1fonic acid,

1-amino-4-(4'-ethoxy)-phenoxybenzene-2-sulfonic acid,

1 amino-4-(5',6',7,8-tetrahydro)-naphthy1(1')-oxybenzene-Z-sulfonicacid,

1 amino-4-(5',6',7',8'-tetrahydro)-naphthyl(2)-oxybenzene-Z-sulfonicacid, etc.

The aforesaid 1 amino-4-phenoxybenzene-2-sulfonic acids (I) can beprepared from the corresponding 1-amin0-- 4-phenoxybenzenes,advantageously by heating the acid sulfates thereof to hightemperatures.

Illustrative of the 2-phenylamin0-8-hydroxynaphthal-- ene-6-sulfonicacids of Formula II which are suitable as azo components in thepreparation of the dyestuffs of the present invention are inter alia:

2-(2',6'-dimethyl) -phenylamino-8-hydroxynaphthalene-6- sulfonic acid,

2 (2',3,4',6'-tetramethyl)-phenylamino-8-hydroxyriaphthalene-6-sulfonicacid,

2 (2',6'-dimethyl-4-methoxy)-phenylamino-8-hydroxynaphthalene-6-sulfonicacid,

2 (2',4',6'-trimethyl)-phenylamino-8-hydroxynaphthalene-6-sulfonic acid,etc.,

the latter being the preferred azo component.

The coupling of the diazo compounds with theZ-phenylamino-8-hydroxynaphthalene-6-sulfonic acids of formula (II) iscarried out in acid medium; coupling takes place at the 1-position ofthe azo component. To this end, the cold hydrochloric acid suspension ofthe diazo compound is combined, in the presence of an alkali metalacetate, with the aqueous solution of theZ-phenylamino-S-hydroxynaphthalene-6-sulfonic' acid (II) whichpreferably is at room temperature (about 15 to about 30 C.). Thecoupling mass is stirred for some time at room temperature after whichthe formed monoazo dyestui'r is filtered 01f, if necessary after theaddition of sodium chloride to the coupling mass, and then the filtereddyestufi? is purified--if necessary by reprecipitation from hot wateranddried.

The new acid monoazo dyestuffs thus prepared according to this inventioncorrespond to the formula I SOaH HO SOaH (III) previously-indicatedsignificances. They are red powders which dissolve with-red. colorationin water and which dye wool, silk and synthetic polyamide fibers such e.g. as nylon from a neutral to weakly acid bath in bluish red shades. Thedyeings posand good to very good fastness to Washing, perspiration,alkaline fulling and acid fulling. The monoazo dyestuffs prepared fromthe diazo components according to the invention and 2-(2,-4,6'-trimethyl)phenylamino 8 hydroxynaphthalene 6- sulfonic acid arefurther distinguished by the remarkable purity of their dyeings.

The following examples set forth representative embodiments of theinvention, these being entirely illustrative and not at all limitative.In these examples, the parts and percentages are by weight; thetemperatures are in degrees centigrade.

EXAMPLE 1 33.4 parts of1-amino-4-[2',4-dichloro)-phenoxybenzene-Z-sulfonic acid are dissolvedin 300 parts of water with the addition of sodium hydroxide in the formof sodium salt. After admixture thereof with 40 parts of aqueous sodiumnitrite solution of 20% strength, the resultant solution is run into awell-stirred mixture of 40 parts of concentrated sulfuric acid, 200parts of water and 100 parts of finely crushed ice. After stirring themass for one hour at -10", the diazo compound which separates out isfiltered off and stirred into the form of a pulp with 200 parts of icewater. The thus-produced suspension is then combined, while stirringthoroughly, with a solution, at -20", of 36 parts of2-(2',4',6'-trimethyl)-phenylarnino-8-hydroxynaphthalene 6 sulfonic acidin 400 parts of water and 30 parts of crystalline sodium acetate. Afterstirring this coupling mass for three hours, the monoazo dyestuff whichis produced is salted out with 50 parts of sodium chloride, and thenfiltered off and dried. It corresponds to the formula NH GH:

( 31 S OLH HO s osH and is a red powder which dissolves with bluish-redcoloration in warm water, and dyes wool, silk and synthetic polyamidefibers from a weakly acid bath in pure bluish-red shades of very goodfastness to light and good fastness to washing, perspiration andfulling.

EXAMPLE 2 37.7 parts of 1-amino-4-(4'-iso-octyl)-phenoxybenzene-2-sulfonic acid are indirectly diazotized according to the procedure setforth in Example 1. The precipitated diazo compound is filtered off andstirred together with 350 parts of ice water. The resultant suspensionis admixed, while stirring thoroughly, with a solution-having atemperature of 10-15-of 36 parts of 2-(2',4',6'-trimethyl)phenylamino-8-hydroxynaphthalene-fi-sulfonic acid in 600 parts of waterand 35 parts of crystalline sodium acetate. After stirring the couplingmass for about four hours, the precipitated monoazo dyestuif is filteredoff, if desired purified by reprecipitation from hot water, and thendried. It corresponds to the formula NH CH5 SOIH HO and is a red powderwhich readily dissolves with bluishred coloration in hot water and whichdyes wool, silk and synthetic polyamide fibers from a neutral bath inpure bluish-red shades of very good fastness to light and very goodfastness to washing, perspiration and fulling.

The following table sets forth additional examples of monoazo dyestuffsaccording to the present invention, which can be prepared after themanner described in the foregoing examples. Column 1 of the table setsforth the number of the examples, while column 2 sets forth thel-amino-4-phenoxybenzenes of Formula I, and column 3 sets forth theZ-phenylamino-8-hydroxynaphthalene-6-sulfonic acids of Formula IIinvolved in making the corresponding acid monoazo dyestuffs according tothe present invention. These dyestuffs yield, in each of the examples,dyeings which are bluish-red in color.

Table 3 i -amiuo 4 phencxybcnzenc- 2 (4 methyl) -phenylamino 4 2sulfonicacid. 8 hydroxynaphthnlcnc ti sulionic acid.

4 .do 2 (4-mcthoxy)-phcnylarnin0- 8 hydroxynaphthalcne 6 sulfonic acid.

5 s ..r do 2 (2', 4 -dimethyl) phenylarnino 8 hydroxynaphthalene 6sullonie acid.

6 do 2 (2,5' dirncthyl) phenylarnino 8 hydroxynaphthalene 6 sullonicacid.

7 .do 2 (2,6 dimcthyl) phenylarnino 8 hydroxynaphthalenc 6 sull'onicacid.

8 do 2 (2',5 dicthoxy) phenylamino S hydroxynaphthalene 6 sultonic acid.

9 do 2 (4' chloro) phenylarnino 8 hydroxynaphthaleue 6 sulionic acid.

10 do 2 (5,6,7,8 tctrahydro) naphthylfl) amino 8 hydroxynaphthalene 6sulfonic acid.

11 do 2 (5,6,7,8 tetrohydro) naphthyKZ) amino 8 hydroxynaphthalene 6sulfonic acid.

12 1 amino 4 (2,4 dichloro) 2 (4 methyl) phcnylamino phenoxybenzene 2sul 8 hydroxynaphthalenc 6 fonic acid. sulionic acid.

13..." 1 amino 4 (2,4,5' tri- Do. chloro) phenoxybenzene 2-su1fonicacid.

14"... 1-amino-4-(4-iso-octyl)- Do. phenoxybenzenc 2 s tonic acid.

15 1 amino 4 (4 phenyl) Do. phenoxybenzene 2 sul-. tonic acid.

16 d0 2- (2,4,6 -trimcthy1) -phenylamino 8 hydroxynaphthalene 6 sulfonicacid 17... 1 amino 4 (4 benzyl) Do. phenoxyhenzene 2 sul Ionic acid.

18..." 1-amino-4-(4-tert.amyl)- Do. phenoxybcnzene 2 sulfonic acid.

19 1 -amino -4- (4 cyclohexyl) Do. phenoxybcnzene 2 sulfonic ac 20.l-aminot- (2,4-dimethyl)- 2 (2, 3, 4, 6 tetramethyhphenoxybcnzene 2sulphenylamino 8 hydroxytome acid. nnplhthalenc t3 sulfonic aei 1 amino4 (2 mcthoxy 5'- 2 (3 chlorn) phenylamino methyl) phenoxyhenzene 8hydroxynaphthalenc 6 2-sn1fonic acid. sull'onic acid.

1 amino-4 (5,6,7,8' tetra- 2 (2', 6 dimothyl) phenylhydro) naphthyl( 2)oxyamino 8 hydroxynaphthabenzene 2 sulfonic acid. lene-fi-sulionic acid.

23..-" 1 amino 4 (2,5 diethoxy)- 2 (2,4,6trimethyl)-phenylphenoxybenzeno 2 sulamino S-hydroxynaphthm tom'c acid.lene-fi-sultonic acid.

24... 1-amino-4-(3-fluoro) -phe- Do. noxybenzcne 2 sulfonic act 25. 1-amino 4 phenoxybenzene- 2 (4 -fluoro) phenylamino -8- 2-sulfon1c acid.hydroxynaphthalene 6 sulfomc acid.

Representative of the monoazo dyestuffs of the foregoing table are thoseof Examples 16, 18 and 19, the 2. An acid monoazo dyestufi whichcorresponds to the formulae of which are respectively as follows:formula 3 01- O N=N SOaH HO 80311 S H 3. An acid monoazo dyestuif whichcorresponds to the formula EXAMPLE 18 OH;

CH; HwOoG-Nm H o o- -N= I SOIH HO $10511 30,11 4. An acid monoazodyestuff which corresponds to the I I formula EXAMPLE 19 OH:

NH -CHs NH -OH:

OH OH on, 130 -O--N=N I \GHZOHQ A SOzH HO OaH HO I S0311 $0111 5. Anacid monoazo dyestufi which corresponds to the EXAMPLE 26 fmmula CH 100parts of wool are entered into a dyebath contain- I 3 ing 1 part of thedyestufl obtainable according to Ex- NHOQIQ ample 1, 10 parts of sodiumsulfate, 2 parts of acetic acid and 8000 parts of water, at 4050. Thebath is heated to boiling, kept at boiling temperature for 30 minutes,and then cooled to about 70 whereupon an H1105 additional 2 parts ofacetic acid are added. The bath l is then again heated to boiling for 30minutes. The SOEH Wool is withdrawn, rinsed and dried; it is dyed in afast, pure bluish-red shade. SIOSH Synthetic polyamide fibers and silkare dyed in analogou-s manner, although in the case of the latter the fand monazo dyestufi which corresponds to the bath is not heated toboiling but only to 90-95 0 Having thus disclosed the invention, What isclaimed is: (3H3 1. An acid monoazo dyestuff which corresponds to theformula G- NH-Rz I /CH2CH2 om HaO-O-N=N \OH 43% Sean H0 5 a 9 soirr H0SOaH SOsH

wherein R1 stands for a member selected from the group consisting ofphenyl, fluorophenyl, chlorophenyl, lower References Clted m the file ofthls patent alkylphenyl, cyclo-alkylphenyl, aralkylphenyl, lower 7 0NITED STATES PATENTS yp y lower y yp y ph ny and 2,5 Fell-X et a1 g 11,1933 5,6,7,8-tetrahydronaphthyl, and R2 stands for a member 2,150,737 sh lti et a1 Man 147 1939 selected from the group consistin offluorophenyl, chlorophenyl, methylphenyl, lower al l coxyphenyl and5,6,7,8- FOREIGN PATENTS tetrahydronaphthyl. 424,355 Great Britain Feb.20, 1935

1. AN ACID MONOAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA